Prevention of cold flow in polymers of conjugated dienes



United States Patent 3,393,182 PREVENTION OF COLD FLOW IN POLYMERS 0F CONJUGATED DIENES William J. Trepka, Bartlesville, Okla, assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Filed Feb. 23, 1965, Ser. No. 434,659 19 Claims. (Cl. 26079.5)

ABSTRACT OF THE DISCLOSURE Polymers of conjugated dienes are made by polymerizing monomers containing at least one conjugated diene with an organoalkali metal initiator. At the completion of the polymerization reaction, the polymerization reaction mixture is terminated with a reactive tin compound having reactive sites.

This invention relates to an improved process for preparing conjugated diene polymers. In one aspect it relates to a process for preventing or substantially reducing the tendency of certain conjugated diene polymers to cold flow. In another aspect it relates to polymers of conjugated dienes having a reduced tendency to cold flow.

In recent years there has been a great deal of research with the object of producing improved rubbery polymers of conjugated dienes. One of the products that has attracted wide-spread attention because of its superior properties is polybutadiene. The physical properties of these polymers are of such a nature that they are particularly suitable for the fabrication of automobile and truck tires and other articles for which conventional synthetic polymers have heretofore been comparatively unsatisfactory. However, it has been found that certain of the conjugated diene polymers, including copolymers of conjugated dienes and various other compounds such as vinyl-substituted aromatics, have a tendency to cold flow while in the unvulcanized or uncured state. Because of the tendency to cold flow, handling and processing of the unvulcanized polymers present many difiiculties. In some instances, cracks or punctures in packages containing the uncured or unvulcanized polymer result in product loss or contamination as a result of the cold flow. While it is possible to cross link the molecules of the polymers, such as is done by conventional curing, in order to eliminate cold flow, this approach cannot be employed in cases where the polymers must later be compounded in masticating equipment. The formation of relatively large amounts of gel as a result of cross linking greatly reduces the ease with which the polymers can be mixed with other materials in fabricating. Accordingly, it is highly desirable to provide a method for reducing the tendency of these polymers to cold flow without increasing the difiiculty of processing in conventional masticating equipment.

It is an object of this invention to provide an improved process for producing polymers of conjugated dienes that have a reduced tendency to cold flow.

Another object of this invention is to provide a process for producing polymers of conjugated dienes having improved processability.

Still another object of this invention is to provide improved jugated diene polymers having a reduced tendency to cold flow in the unvulcanized state and an improved processability.

Other aspects, advantages, and objects of this invention "ice will become apparent to those skilled in the art upon consideration of the accompanying disclosure and claims.

The present invention is concerned with the production of improved conjugated diene polymers which have a reduced tendency to cold flow. Thus, the invention resides in an improvement in a process for polymerizing conjugated dienes with a catalyst system comprising an organo alkali metal compound. Broadly speaking, the improvements comprise the step of adding to the polymerization mixture a compound having the formula: R SnZ wherein R is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic, aromatic radicals, and combinations thereof, Z is selected from the group consisting of fluorine, chlorine, bromine, iodine,

-OR", -SR, :0, =8, O-R"O and -SR"S wherein R is selected from the group consisting of hydrogen, saturated aliphatic, saturated cycloaliphatic and aromatic radicals and combinations thereof, R" is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals and combinations thereof, R" is an alkylene radical With which the oxygen or sulfur and the tin atom forms a cyclic compound containing from 5 to 8 members in the ring and when Z is selected from the group fluorine, chlorine, bromine, iodine, R-CH=CHCH OR" and -SR", x is an integer from 0 to 2 and y is an integer from 2 to 4 such that x plus y equals 4, and when Z is =8, :0, -OR'"O or S-R" y is l and x is 2. The number of carbon atoms in each of R, R and R" is in the range of 1 to 12. The number of carbon atoms in R' is in the range 2 to 12. R, R and R" can be the same or different. It has been found that by adding the treating agent of this invention to the polymerization mixture, after the polymerization has been completed and prior to the inactivation of the catalyst, the rubbery product obtained has a reduced tendency to cold flow. The product also is processed very easily on conventional masticating and compounding equipment as described hereinafter.

EXarnples of the tin compounds that can be utilized in this invention are:

stannic fluoride stannic chloride stannic bromide stannic iodide tetraallyltin methyltrichlorotin di-n-hexyldifluorotin dodecyltn'iodotin dodecyltrichlorotin dicyclohexyldichlorotin diphenyldibromotin benzyltrichlorotin 4-tolyltrifiuorotin diethyldiallyltin propyltriallyltin diallyldichlorotin dodecylallyldichlorotin tetra(2-octenyl)tin tetra(3-cyclopentyl)allyltin dibutyldimethoxytin tetramethoxytin dibutylbis (octyloxy)tin di benzyloxy) diethyltin tri(dodecoxy)cyclohexyltin di (cyclopentoxy) diphenyltin tetradodecoxytin dichlorodiphenoxytin tetramethylthiotin di( dodecylthio) diphcnyltin tri(butylthio)cyclopentyltin di(benzylthio) didodecyltin tri(cyclohexy1thio)nonyltin tetradodecylthiotin dirnethyltin oxide di(3-diphenyl)tin oxide dibutyltin oxide dicyclohexyltin oxide didodecyltin oxide butylphenyltin oxide dimethyltin sulfide dibutyltin sulfide di-p-biphenylyltin sulfide didodecyltin sulfide di-l-naphthyltinsulfide dicyclopentyltin sulfide 2,2-dibutyl--methyl-1,3-dioxa-2-stannacyclopentane 2,2-diethyll,3-dioxa-2-stannacyclohexane 2,2-di (4-tolyl) -l,3-dioxa-2-stannacycloheptane 2-ethyl-2-phenyl-S-butyl-1,3-dioxa-2-stannacylohexane 2,2-dipropyl-1,3-dioxa-2-stannacyclooctane 2,2-dimethyl-l,3-dithia-2-stannacyc1opentane 2,2-didodecyl-1,3-dithia-2-stannacyclohexane 2,2-diphenyl-4,5,6,7-tetramethyl-1,3-dithia-2-stannacycloheptane 2,2-dibutyl-4,4-dimethyl-1,3-dithia-2-stannacyclopentane Some of the above-mentioned tin compounds may exist in a polymeric form. When the tin compounds are in polymeric form, additional mechanical mixing steps known in the art may be required to insure intimate contact between the tin compound and the alkali metal terminated polymer.

The polymers which can be prepared according to this invention are broadly polymers of conjugated dienes, more specifically conjugated dienes containing from 4-12 carbon atoms per molecule, and preferably those which contain from 4-8 carbon atoms per molecule. Examples of these monomers include: 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,3-octadiene, 4,5- diethyl-l,3-octadiene, and the like. These conjugated dienes can be polymerized to form homopolymers or they can be copolymerized one with another. Conjugated dienes can also be copolymerized with one or more monovinylcontaining monomers such as styrene and alkyl styrenes, e.g., 3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, 2,4,6-trimethylstyrene, 3-methyl-5-n-hexylstyrene, 2,3,4,5- tetramethylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 4 phenylstyrene, 4-p-tolylstyrene, and the like.

The conjugated dienes can also be copolymerized with other monovinyl-containing monomers such as: l-vinylnaphthalene, 2-vinylnaphthalene, 4-methyl-l-vinylnaphthalene, 3-ethyl-2-vinylnaphthalene, 4,5-dimethyl-l-vinylnaphthalene, 4,5-diethyl-2-vinylnaphthalene, 6-isopropyll-vinylnaphthalene, 2,4-diisopropyl-l-vinylnaphthalene, 4- n-propyl-S-n-butyl-2-vinylnaphthalene, and the like. When copolymers of conjugated dienes and monovinyl-containing aromatic compounds are formed, it is preferred to have a major amount of conjugated dienes and a minor amount of the monovinyl-containing aromatic compounds in the polymerization system.

The polymers of the above-listed compounds are prepared by contacting the monomer or monomers which it is desired to polymerize with an organoalkali metal compound, including mono and polyalkali metal compounds in the presence of a hydrocarbon diluent. The organoalkali metal compounds preferably contain from 1 to 4 alkali metal atoms per molecule. While organometallic compounds of any of the alkali metals can be employed, organolithium compounds are preferred. The alkali metals include lithium, sodium, potassium, rubidium, and cesium.

The organoalkali metal compounds that are used as catalysts can be prepared in several Ways, for example, by replacing halogens in an organic halide with alkali metals, by direct addition of alkali metals to a double bond, or by reacting an organic halide with a suitable alkali metal compound.

Suitable organoalkali metal initiators can be represented by the formula RM wherein R is a hydrocarbon radical selected from the group consisting of aliphatic, cycloaliphatic, and aromatic radicals containing from 1 to 20 carbon atoms, M is an alkali metal, and x is an integer from 1 to 4. The preferred initiators are organolithium compounds wherein x is 1 or 2. Examples of the organoalkali metal compounds that can be used as catalysts include:

methyllithium n-butyllithium tert-butyllithium amylpotassium isopropylcesium n-decyllithium phenyllithium l-naphthyllithium 1,4-dilithiobutane 1,5-dipotassiopentane 1,4-disodio-2-methylbutane 1,6-dilithiohexane 1,10-dilithiodecane 1,15-dipotassiopentadecane 1,20-dilithioeicosane 1,4-disodio-2-butene 1,4-dilithio-2-methyl-2-butene 1,4-dilithio-2-butene 1,4-dipotassio-2-butene dilithionaphthalene 1,4-dilithiomethylnaphthalene disodionaphthalene 4,4-dilithiobiphenyl disodiophenanthrene dilithioanthracene 1,2-di1ithio-1,l-diphenylethane 1,2-disodio-1,2,3-triphenylpropane 1,2-dilithio-1,2-diphenylethane 1,2-dipotassiotriphenylethane 1,2-dilithiotetraphenylethane 1,2-dilithio-1-phenyl-l-naphthylethane 1,2-dilithio-1,2-dinaphthylethane 1,Z-disodio-1,1-diphenyl-Z-naphthylethane l,2-dilithiotrinaphthylethane 1,4-dilithiocyclohexane 2,4-disodioethylcyclohexane 3,5 -dipotassio-n-butylcyclohexane 1,3,5 -trilithiocyclohexane 1-lithio-4-(2-lithiomethylphenyl)butane 1,2-dipotassio-3-phenylpropane 1,2-di (lithiobutyl)benzene 1,3-dilithio-4-ethylbenzene 1,4-dirubidiobutane 1,8-dicesiooctane 1,5,12-trilithiododecane 1,4,7-tn'sodioheptane 1,4-di l ,2-dilithio-2-phenylethyl) benzene 1,2,7 ,8-tetrasodionaphthalene 1,4,7,IO-tetrapotassiodecane 1,Z-disodio-1,2-diphenylethane dilithiophenanthrene 1,2-dilithiotriphenylethane 1,2-disodio-1,Z-diphenylethane dilithiomethane 1,4-dilithio-1, 1,4,4-tetraphenylbutane 1,4-dilithio-1,4-diphenyl-1,4-dinaphthylbutane and the like.

The amount of initiator used depends upon the organoalkali metal compound and the type of polymer desired. The effective initiator level is normally in the range of about 0.25 to 20 millimoles per 100 grams of monomer(s) atom of alkali metal in the initiator. One equivalent of the reactive Z group per gram atom of alkalimetal in the catalyst is most preferred for maximum reduction in the cold flow and improvement in processability of the polymer.

harged to the polymerization system. Organoalkali metal 5 As indicated above, one of the advantages of using this initiators vary greatly in their solubility and this has a yp of compound to reduce cold flow in the Conjugated considerable ff t on the amount used, Compounds hi h diene polymers is the improved processability of the polyare very soluble in hydrocarbon diluents, such as butyli Was unefipected t0 find that when the l flow lithium, amyllithium, and the like, are used in relatively conlllgated dlef1e P Y Was defea$ed 1 15mg the mall amounts, i.e., amounts in the lower portion of the 10 tin compounds of this invention, the processability of the specified range. Those which possess limited solubility can treated P y Was not degraded- It Well known to be used in larger amounts, the least soluble compounds f l the terfdency of Polymers to cold flow cross being used in the larger quantities. In any event the hflkmg but thls usually P F a 15 Very initiator level is generally adjusted, together with the tin dlfficult Process- Durmg mlnmg Operanons m {ubber compound, to yield a polymer with an inherent viscosity 15 f P l Steps the Polymers Produced achordmg to this invention are very easily processed and give a final in the range of 1.0 to 3.5.

It is Preferred that the p 01 ymerization be conducted in rubber stock which exhibits vulcanizate properties that the presence of a suitable diluent such as benzene, toluene, hbquwalent g superor to of i i h have xylene, Cyclohexane, methylcyclohexane, n-butane, nno i h d L CO 8 hslhg h i hexane n-heptane, isooctane, mixtures of these, and the pohh S 15c 05h ehhlh e found. t at PO ymers treated according to my invention having reduced Generally the dhheht Selected from h h h tendency to cold flow are characterized by a relatively paramns cyclopamihhs alromahcs cohthhhhg high Mooney viscosityfUpon subsequent milling and comfrom to 10 Carbon i h per mo ecu pounding operations, when mildly acidic compounds are Whlle the Polymerlzatlon temperanjre Y g or present, the Mooney viscosity decreases to a level wherebroad range from 9 to 150 It 15 pm by the polymer is very easily processed with conventional to operate at a temperature in the range of 75 to 75 equipment Q penoh reqhlred for phlymenzhhloh and for s The following examples are included to illustrate prehoh the hh .compohhd with the i can =i ferred embodiments of my invention. Material included h h h 5 mlhhtes to 100 hours Ough the time Is in the examples should not be interpreted as unduly limitol'dlnafny 1n the {ange of about 10 f to hours ing the scope of the invention as hereinbefore described. uaxii'llg l i r r l e igi gst 5 12 5;PFZZSQQHIS EISZZZ EZEYE Q Z: Footnotes describing test procedures used in the examhon dioxide, oxygen, water, alcohols, mercaptans, and P165 are Shown at the conclusion of Table primary and secondary amines. It is highly desirable, EXAMPLE 1 therefore, that the monomers be freed of these materials The following recipe was employed in a Series of runs as well as other materials which tend to inactivate the for the preparation of polybutadiene Containing carbon. catalyst. Any of the well known means for removing tin bonds such contaminants can be used. Also, it is preferred that h lv mixture used in the process be substantially 13'butad1ene Parts by wefght 100 f of impurities such as water, oxygen, and the like. 40 h h parts by wfilght I his connection, it is desirable to remove air and mois- Y P mmoles varlable ture from the reaction vessel in which the olymerization stfmmc chloride, 1111110168 Variable i onducted. Any reactive impurities remaining in the Tune hours reaction vessel or in the solvent mixture are removed Tempenituret 122 by the organoalkali metal catalyst which serves as a converslonipercent 100 scavenger. Cyclohexane was charged first, the reactor was purged y pp p regulation Of the catalyst level d the with nitrogen, and butadiene was added followed by the tin compound, products ranging from relatively low molec- -butyllithium. The temperature was maintained at 122 ular weight, soft, easily processable rubbers to relatively F d i polymerization Conversion was quantitative high 1 nl Weight polymers can be obtained. In cases after a 3-hour period. Stannic chloride was added and the where a high inherent viscosity rubber is desired, this intemperature wa aintai ed at 122 F, fo 16 hour The vention is very useful in producing such a product withmixture was agitated throughout polymerization and out excessive cross linking and gel formation in such stannic chloride treatment. A solution of 2,2-methyleneproducts. As stated hereinbefore, the process is concerned bi (4-methyl-6-tert-butylphenol) in isopropyl alcohol was generally with preparing polymers having an inherent visadded in an amount to provide one part by weight per cosity 1ijn the rang; oft) 1.0 $013.15 Idowever, the range is 100 weight parts rubber. The polymer was coagulated in not to e construe to e no u y uniting. isopropyl alcohol, separated, and dried. Inherent viscosit Glenerally thef: gigg tn 5f in compougd enployid and cold flow were determined on the original and on m in t e range 0 o equiva en s, ase on t e stannic chloride treated 01 mer. The ori inal and the groups in the formula R SnZ per gram atom of alkali starlnic chloride polynier l Zvere completehy soluble in metal in the initiator. The preferred range for the amount toluene, indicating that they were gel free. Results are of tin compound to be added is from 0.5 to 2 equivalents, presented in Table I. In the table, mhm.=millimoles per based on the Z groups in the formula R SnZ per gram grams monomer.

TABLE I Original Polymer Stannie Chlon'de BuLi Effect ve Such, Terminated Polymer Charged, BuLi rnlirn.

mhm. Level, Inh. Cold Flow, Inh. Cold Flow,

mhm Vise. mgJmiiL Vise. rng./min.

i. 0 0. 4 0. 10 1.66 104 2.80 0 1.2 0. s 0. 15 1. 33 171 2. 44 0 1. 4 0. 3 0. 20 i. 31 357 2. 36 0 1.6 1. 0 0. 25 1. 12 613 2. 18 0 1.3 1. 2 0. 30 1.06 552 1.88 0

1 Assumed scavenger level, 0.6 millimole. For footnotes a and I), see compilation following Table XII.

The data show that stannic chloride is a very efiective agent for reducing cold flow of polybutadiene prepared TABLE IV in the presence of n-butyllithium. Control Milling characteristics of the polymers from runs 1, 2, nated 3 and 5 were studied by milling them on a roll mill. Dif- 5 Compounding Recipe, Parts by Weight: ferent acidic-type materials were added, except in one Polybutadiene 100 100 run, to aid in the processing. Results are summarized in g g i fzii f g Table II. In the table, phr.=parts by weight per 100 gtlearic acid 1 k exannne parts by we1ght polymer. 2 5 21 5 5 roma ie 5 TABLE H :%%s"s""=rr 1 3 1 3 P9012} Original Mined Polymer Raw Polymer P ropertiesz Polymer Polymer, ML-4 at g a 212 3- 51-5 from Run M1r4 at urn Reagent Added 212 F. 3 u 'l 0 Temp, After erent viscosity B 1.95 2.37

o F Type PM 10 min Processing Properties:

' Oompounded ML-4 at 212 F. 57. 5 55. 5

EXtlillSlgD. /at 250 F.: d 43 3 1 73 Cold snort-512120.-. 2 53 95mm 6 2 63 240 Stearic acid 5 49 g m 5 995 105-0 3 69 240 9 Physical l g p ei tieg red 30 Minutes at3 n n 5 61 51 3 ,a h nui 0. 2 0 0 0 us 1, 0 For footnote 0, see compilation following Table I Tengflelvp S i 2, 190 2 330 The data show that the polymers exhlbrted cons1derg EpmP 3 able breakdown on the mill. significant decrease in j'fig j 67,3 5 Mooney occurred in run 5 1n WhlCh no processing and was fi g g i o C i 1 1 added but there was a considerably greater reduction 2 p 5 1 Physical mixture containing 65 percent of a complex diarylaminewhen either stanmc chloride or stea 1c acld was present ketonereaetionproduot and 35 percent of N ,N-diphenyl-p-phenylenediax me. E MP1 E H 2' gisproipoggolnateg 1pale rolslin stlablllelafto heat;i and light. -oxy ie yeneenzot iazy s enami e. A series OI runs was made 111 Vifhl h butadlene was For footnotes aj,se0 compilation following Table XII. polymenzed 1n the presence of vanable amounts of nbutyllithium. Quantitative conversion was obtained after polymerization at 122 F. for three hours. Tetraallyltm was then added and the mixture was agitated for 16 hours Even though the control polymer had lowest while the temperature was maintained at 122 F. Other- Mqoney Value of the two polymers the Processmg propwise the recipe and procedure were the same as in Exam- 6.11168 were not as good as the Stanmc ch10 ple L Control samples wem Withdrawn at each catalyst rlde treated polymer. The stanmc chlorlde treated polymer level and terminated with isopropyl alcohol (not in comexhlblted no F flow and the Yi had hlgher pound used) Inherent Viscosity and cold flow were deter modulus, tensile strength, and reslllence and lower heat mined on each polymer and Mooney values were deterbulld'up than an control Polymermmed on the polymers treated w th tetraallyltln. The EXAMPLE IV polymers were completely soluble 1n toluene, indicating 40 that they were gel free. Results are presented in Table The recipe of Example I, run 2 was employed for the III. polymerization of butadiene in the presence of n-butyl- TABLE III Control Polymer Tetraallyltin Terminated BuLi Eflective Tetra- Polymer Charged, BuLi allyltin mhm. Level, mhm. Inh. Cold Inh. Cold ML-4 at mhm. Vise. Flow, Vise. Flow, 212 F3 mgJmin. mgJmin.

1 As in Table I. For footnotes a, b, and 0, see compilation following Table XII.

These data show that tetraallyltin was very effective in reducing the cold flow of poly butadiene prepared in the presence of an organolithium catalyst.

EXAMPLE III A run was made using the recipe and procedure of run 2 of Example I. Quantitative conversion was obtained. The polymer was completely soluble in toluene, indicating that it was gel free. The polymer was compounded in a tread stock recipe, cured 30 minutes at 307 F. and physical properties determined. A commercial polybutadiene rubber prepared in the presence of an organolithium catalithium. Quantitative conversion was obtained in each run. Stannic chloride was added in the first 11m as previously described but in a second run it was replaced with an equivalent amount (0.15 millimole) of germanium tetrachloride. Both products had zero cold flow. Inherent viscosity and gel were determined on the original polymers. Stearic acid (3 phr.) was milled into each polymer on a roll mill at 240 F. The milling time was 3 minutes. Inherent viscosity and gel were again determined. The polymers containing stearic acid were then put into a press and heated in the absence of air for 6 minutes at 340 F. Inherent viscosity and gel were again determined.

lyst was used as a control. Data are presented in Table IV. Results are reported in Table V.

TABLE V tion formulation together with a butadiene/styrene block copolymer prepared in a similar manner but without treat- 811C111 GeCl Treated Treated ment with stanmc chlorlde. Raw polyer properties, proc- I 1 t ,S St essing properties, and physical properties of the vulcani- 1 gg fgfg g 280 278 zates were deterrnmed. The polymers were completely :Zg i 'p tt ontofstetaric acid. fig 5?; soluble in toluene, indicating that they were gel free. Ge], jg i, Press rea men Data are presented in Table VII.

Original polymer 0 0 After incorporation 01' stearic acid 0 0 TABLE VII After hot press treatment. 0.3 0 C Ont I O1 1 2 For footnotes a and k, see compllation followmg Table )TII. Compounding Recipe, Parts by Weight:

These data show that germanium tetrachloride dld not g 8 improve the processability of the polymers, as evidenced Steat'i ljjjjjj 1O 10 10 by no change in inherent viscosity even after the hot press g ggz g *8 kg kg treatment. The polymer treated with stannic chloride did pm-ecapo Q11: 1 50 50 50 not appear to undergo any change when milled under the g g conditions employed but a significant decrease in inherent I 5 L5 L5 H 0.5 0.5 0.5 viscoslty occurred when it was heated 1n a press n the Raw Polymer Pnqpemes absence of air for 6 minutes. ThlS change is indicatlve 0f um at 212 F. 43 7o 01 Inherent Viscosity 1.81 1.71 cleavage of carbon tin bonds. 2O Procssmg g g g 4 t 9 F ompoun e a -1 32.5 70 61.5 EXAMPLE V Extrusilon at 180 F.: d I 0 es 4.4 7.4 .4 A serles of runs was made for the preparatlon of buta- R E QH E d 1 i 1 mount ating arvey ie 12 11 11 dlene/sLynTe. block copolymers l 8mg ab 3 .5 Physical Properties, Cured 30 Minutes at 307 of n-bntylhthiurn as the catalyst. Converslon was quant1- 1 Cornpressionset,percent: 66.8 34.3 38.8 tat1ve 1n all cases. After a SIX hour reaction penod, stannlc 200% Modulus psi L" 690 690 740 chloride was added 1n half the runs, the others belng reg f n g p s i z 1,150 1, 540 1,410

Q onga ion, percent 665 71 690 served s controls After continuing the reactions for 16 Show Ahardness, 81 82 83 more hours, the products were recovered as in Example I.

a 1 Octylated diphenylamine. The following polymerization recipe was used. ,3 a 11 1? white g f g g d i l mineml fineremica r a 0.15-0.30 c'on; s e- 1,J-butad1ene, parts by weight 75 gravity empl e a 3 p r e 1 p Styrene, parts by weight 25 4 Polymers of eoum arone, indene, and associated coal-tar compOlgndS; cyclohginile, parts by weight gg g pmn 5- 0., m mum s- 0.5%. p m g y n-Butylhtnium, mmoles Variable igenlglihlfigglllgllstlfihfidab t Inc 11118 y 1 1008.1 ama. 8. siaanmc Chlond, mmoles Vanable For footnotes a, e, d, f, i, and I, see compilation following Table XII. Time, hours 6+16 Tern erature F. 122 The data show that even though the olymers treated Cyclohexane was char ed to the reactor first after Wlth Stanmc chlonde had much hlgher .cqmpounded Mooney values than the control, they exh1b1ted better WhlCh it was purged with nitrogen. Styrene was added 40 followed b thg butadiene and then tbs but nithium processablhty as ev1denced by the extrusion data. Com- Data are smifnmarizedin Table VI y pression set data show that they reached a much better state of cure than the control and had a much higher TABLE VI tensile strength. BuLi Charged, Etlective BuLi snol. Inh. ML-4 at EXAMPLE VII mhm. Level, mhm. mhm. Vise. 212 F.

A series of runs was made for the preparation of butakg g S3 38 diene/ styrene random copolymers using variable amounts 2.0 1.4 0 0.98 51.5 of n-butyllithiu-m as the catalyst, Conversion was quankg %:3 8 58 $23 gg-g titative in all cases. After a 1.5 hour reaction period, 2.0 1.4 0.35 1. 41 50.0 stannic chloride was added in all but one run and the 1 Asin mammal reactions were continued for 1.5 more hours. The prod- For footnotes aand 0, see compilation following Table XII. ucts were recovered as in Example I. The following EXAMPLE VI polymerization recipe was used:

Two runs were made in the same manner as runs 5 and 13'butad1ene, Parts Weight 75 6 of Example V. These polymers were prepared for evalu- Styrene Parts by Weight 25 ation purposes. Following are data on polymer preparacyclohexane Parts by We1ght 780 tion. Tetrahydrofuran, parts by weight 1.5

n-Butyllithium, mmoles 1.3 1 2 Stannic chloride, mmoles Variable ndzilityllirtlhium char ed mhm 1.8 2.0 Tlme, hours 'i' Sn 4,rn m 0.30 0.35 Conversion, perc 100 100 Temperature F 122 Cyclohexane was charged to the reactor first after The polymers were compounded in an electrical insulawhich it was purged with nitrogen. Butadiene was added TABLE VIII Milled at 230 F. BuLi Effective SnCli, Inh. ML-4 at with Stearic Acid Charged, BuLi Level, mhm. Vise. 212 F. mhm. mhm. Inh. MLA at Vise. 212 F.

1 As in Example I. For footnotes a. and c, see compilation following Table XII.

1 l 1 2 followed by the SFYIPIIB, thll the tetrahydrofuran, and TABLE 1X' TERMINATIQN OF X 15 WITH BUTYLTRI. finally the n-butylhthlum. The polymers were completely C O ROTIN soljubdle in tfoluenehData are presenteg Table dVIII. h BuLid B S 1 TBeiqre Aft Termination u glng rom in erent viscosity an ooney ata, t e C a g u 3. e optimum effect of stannic chloride in the copolymer mhm'l mhm e i occurred when the millimoles of lithium and chlorine in 1 3 o 1 31 1 28 3 449 the system were equivalent, i.e., a ratio of 1/l. 3 M65 9&0

Processability of the polymers was studied by milling 0.130 1 31 21 3 hr of stearic acid into each 01 mer on a roll mill 0'230 46 Q08 P P Y 1.3 0.350 1.35 2. 29 94 0 at 230 F. for 6 minutes and then determining inherent 1O 8-28 53 2 2% g 52 viscosity and Mooney values. These data, also presented in Table V111, show that under the conditions employed, 'Assumedscaveneerlevel, 0.6mil1imq1ea reduction in inherent viscosity and Mooney values For footnotes a,b, and 0, see compilation following Table XII. I curred upon milling the stannic chloride treated polymers. These l Show that butyltrlchlorPtm y efllfictlve 15 for reducing cold flow of polybutadiene prepared in the EXAMPLE VIII presence of n-butyllithium.

A series of runs was made in which polybutadiene con- EXAMPLI? IX taining carbon-tin bonds was prepared. The following: A series of runs was made using the same procedure as recipe was used: 2 outlined in Example VIII except that the butyllithium 0 was added in an amount of 1.25 millimoles. Instead of 1,3-butadiene, parts by weight 100 using butyltrichlorotin as a treating agent, dichlorodi- Cyclohexane, parts by weight 7-80 octyltin was added. After the treated polymer samples n-Butyllithium, mmoles 1.3 were recovered, inherent viscosity, Mooney viscosity, Butyltrichloro tin Variable and cold flow were determined. They were then milled Time, hours 3+3 at a temperature of 230-240" F. with three parts by Temperature, -F. 122 weight per hundred weight parts rubber of stearic acid Conversion, percent 100 for 6 minutes. The following properties were determined:

TABLE X Inherent Viscosity Mooney ML-4 at 212 F." Cold Flow b BuLi, Rzsnom mhm. mhm. Before After Before After Before After Stearie Stearie Change Stearic Stearic Change Stearic Stearic Change Acid Acid Acid Acid Acid Acid 1. 25 0 2. 07 1. s4 -0. 23 23. 0 17. 5 -5. 5 29. 7 29. 0 -0. 7 1. 25 0. 20 2. 42 2. 07 -0. 49. 0 33. 5 15. 5 12. 3 12.3 +0. 5 1. 25 0. 25 2. 75 2. 19 -0. 56 so. 5 43. 0 37. 6 9. 17 4. s3 -4. 34 1. 25 0.35 2. 51 2. 1s -0. 43 73. s 42. 0 31. 9 9. 63 5. 10 -4. 53

l Assumed scavenger level, 0.6 millimole.

For footnotes a, b, and 0, see compilation following Table XII.

Cyclohexane was charged first, the reactor was purged with nitrogen, and butadiene was added followed by the n-butyllithium. The temperature was maintained at 122 F. during polymerization. Conversion was quantitative after a 3-hour period. Butyltrichlortin was added and the temperature maintained at 122 F. for 3 hours. The mixture was agitated through the polymerization and the butyltrichlorotin treatment. A solution of 2,2-methylenebis(4-methyl-6-tert-butylphenol) in isopropyl alcohol was added in an amount to provide one part by weight per hundred weight parts rubber. The polymer was coagulated in isopropyl alcohol, separated, and dried. Inherent viscosity and cold flow were determined on the original and butyltrichlorotin treated polymers. No gel was observed in any of the polymer samples. Results are presented in Table IX.

A series of runs was made using the procedure outlined in Example VIII above. The only change was in the use of dibutyltinsulfide instead of butyltn'chlorotin. After the polymer samples were recovered and the inherent viscosity, Mooney viscosity, and cold flow were determined, they were milled for 6 minutes at 230240 F. with three parts by weight per hundred weight parts rubber of stearic acid. The results are reported in Table XI.

TABLE XI BuLi, R2Sl'lS, Inherent Viscosity B Mooney, ML-4 at 212 F. Cold Flow, mg./min.

mhm. mhm.

Before After Change Before After Change Before After Change 1. 3 0 1. 86 1. 68 0. 18 r 18. 5 14.0 -4. 5 54. 5 75.0 20. 1. 3 0.30 2. 35 2. 06 0. 29 40. 5 33. 5 16.0 22. 8 18.8 -4.3 1. 3 0.35 3. 10 2. 47 -O. 63 61. 0 44. 0 6. 7O 7. 05 +0. 35 l. 3 0. 40 2. 82 2. 39 0. 43 82. 0 60. 0 -22. 0 8. 53 14. 2 +5. 67 1. 0. 50 2. 58 2. 29 -0. 29 67. 0 49. 5 -17. 5 9. 03 1O. 4 +1. 37

1 Assumed scavenger level, 0.5 milliomole.

2 R2 SnS was added after 3 hours polymerization time; reactiIOIn time was an additional three hours.

For footnotes a, b, and 0, see compilation following Table X These data show that dibutyltinsulfide is effective in reducing the cold flow of polybutadiene prepared with a butyllithium catalyst. They also show that the resulting product is easily processed as evidenced by a substantial decrease in the Mooney viscosity upon millin EXAMPLE XI The following recipe was employed in a series of runs for the preparation of polybutadiene containing carbontin bonds:

Assumed scavenger level, 0.26 mmole; effective initiator level, 0.56 mmole.

The procedure for making the polymers was the same as in Example I. A control run was made in which no tin compound was used. The polymers were completely soluble in toluene. Results of inherent viscosity determinations are presented in the following table:

TABLE XII Run N o. Tin Compound Inh.

Vise.

1 1. 96 Dibutyldirnethoxytin 1 2. 89 Dibutyl(dilaurylthio)tin. 2.87 4 2,2-Dibutyl-5methyl-l,3-dioxa-2-stannacyclo- 2. 80

pentanefl 1 Probably polymeric. 2 Reaction product of dibutyldichlorotin and propylene glycol. For footnote 2:, see compilation following this table.

FOOTNOTES Inherent viscosity was determined by placing one-tenth gram of polymer in a wire cage made from 80 mesh screen and the cage was placed in 100 ml. of toluene contained in a wide-mouth, d-ounce bottle. After standing at room temperature (approximately 77 F.) for 24 hours, the cage was removed and the solution was filtered through a sulfur absorption tube of grade C porosity to remove any solid par ticles present. The resulting solution was run through a Medalia type viscometer supported in a 77 F. bath. The viscometer was previously calibrated with toluene. The relative viscosity is the ratio of the viscosity of the polymer solution to that of toluene. The inherent viscosity is calculated by dividing the natural logarithm of the relative viscosity; by the weight of the soluble portion of the original samp e.

Cold flow, mg./min., was determined by extruding the rubber through a 4-inch orifice at 3.5 p.s.i. pressure and a temperature of 50 C. (122 F.). After allowing 10 minutes to reach steady state, the rate of extrusion is measured and reported in milligrams per minute.

Mooney viscosity, ML4 at 212 F. was determined using procedure ASTM D-1646-61 (Mooney Viscometer, large rotor, 212 F., 4 minutes).

Extrusion at 250 F. was determined using No. /3 Royle Extruder with Garvey die by the procedure described in Ind. Eng. Chem. 34, 1309 (1942). As regards to the rating figure, 12 designates an extruded product considered to be perfectly formed whereas lower numerals indicate less perfect products.

Cross linking, V1, is reported as the volume fraction of polymer in swollen stock, determined by method of Kraus as given in Rubber World. 135, 67-73, 254-260 (1956).

f Modulus, Tensile and Elongation were determined by the method of ASTM D-llZ-Gl'l.

Heat build-up. AT, F., was determined by the ASTM 13-623-58, Method A, using Goodrich Flexometer, 143 p.s.i. load, 0.175 inch stroke. The test specimen was a right cylinder 0.7 inch in diameter and 1 inch high,

Resilience, percent, was determinel by ASTM D-945-59 (modified) using a Yerzley oscillograph. The test specimen was a right cylinder 0.7 inch in diameter and 1 inch high.

1 Shore A hardness was determined by ASTM D1706-61, Shore Durometer, Type A.

I Gehman freeze point, 0.. determined by ASTM D1053 61 using a Gehman torsional apparatus. The test specimen was 1.625 inches long, 0.125 inch wide, and 0.077 inch thick. The angle of twist was measured at C. intervals and the freeze point was obtained by extrapolation to zero twist.

Gel, percent, was determined along with the inherent viscosity determination. The wire cage was calibrated for toluene retention in order to correct the weight of swelled gel and to determine accurately the weight of dry gel. The empty cage was immersed in toluene and then allowed to drain three minutes in a closed widemouth, two-onnce bottle. A piece of folded. 4inch hardware cloth in the bottom of the bottle supported the cage with minimum contact. The bottle containing the cage was weighed to the nearest 0.02

gram during a minimum 3-minute draining period after which the cage was withdrawn and the bottle again weighed to the nearest 0.02 gram. The difference in the two weighings is :the weight of the cage plus the toluene retained by it, and by subtracting the weight of the empty cage from this value, the weight of toluene retention is found, i.e., the cage calibration. In the gel determination, after :the cage containing the sample had stood for 24 hours in toluene, the cage was withdrawn from the bottle with the aid of forceps and placed in the 2-ounce bottle. The same procedure was used for calibration of the cage. The weight of swelled gel when present is corrected by subtracting the cage calibration.

1 Compression set, percent, was determined by ASTM D-395-61, Method B (modified). Compression devices were used with 0.325-inch spacers to give a static compression for the -inch pellet of 35 percent. Test run for 2 hours at 212 F. plus relaxation for 1 hour at 212 F.

These data show that treatment with the tin compounds gave a significant increase in inherent viscosity as in EX- ample X.

As many possible embodiments may be made without departing from the scope thereof, it is understood that all matter herein set forth is to be interpreted as illustrative and'not in a limiting sense.

I claim:

1. In a process for making a polymer wherein a polymerization mixture is formed by polymerizing monomers selected from the group consisting of conjugated dienes and conjugated dienes in admixture with vinyl substituted aromatic compounds, with an organo alkalimetal catalyst, the improvement which comprises terminating the polymerization reaction by adding to said polymerization mixture a compound having the formula R SnZ wherein R is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, RCI-l:CHCH OR", SR", =8, :0, -OR'O and -SR"'S, wherein R is selected from the group consisting of hydrogen, saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R" is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R'" is an alkylene radical with which oxygen and sulfur form a cyclic compound with the tin atom, said cyclic compound containing from 5 to 8 members in the nucleus, the number of carbon atoms in each of R, R and R" being in the range of 1 to 12, the number of carbon atoms in R" being in the range of 2 to 12, when Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, R'CH==CH--CH and SR", x is an integer from 0 to 2 and y is an integer such that x+y=4, and when Z is selected from the group consisting of i, O, 'O-- and S--R"'S, y is 1 and x is 2; and recovering a polymer having a reduced tendency to cold flow in the unvulcanized state.

2. In a process for making a polymer wherein a polymerization mixture is formed by polymerizing 1,3-buta diene with an organo alkalimetal catalyst, the improvement which comprises terminating the polymerization reaction by adding to said polymerization mixture a compound having the formula: R SnZ wherein R is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, R'--CH=CHCH --OR, SR", i, =0, 0-- "'-O and -SR-S-, wherein R is selected from the group consisting of hydrogen, saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R" is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R is an alkylene radical with which oxygen and sulfur form a cyclic compound with the tin atom, said cyclic compound containing from 5 to 8 members in the nucleus, the number of carbon atoms in each of R, R, and R being in the range of l to 12, the number of carbon atoms in R' being in the range of 2 to 12, when Z is selected from the group consisting of fluorine, chlorine, bromine,

1 5 iodine, R'-CH=CHCH -OR", and -SR", x is an integer from to 2 and y is an integer such that x+y='4, and when Z is selected from the group consisting of =S, =0, O-R"O and -SR-S, y is 1 and x is 2; and recovering a polymer having a reduced tendency to cold flow in the unvulcanized state.

3. In a process for making a polymer where-in a polymerization mixture is formed by polymerizing 1,3-butadiene and styrene with an organo alkalimetal catalyst, the improvement which comprises terminating the polymerization reaction by adding to said polymerization mixture 2. compound having the formula R SnZ wherein R is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, R'-CH=CH--CH R", SR", ='-S, =0, O'R"'O and =S-R"'S, wherein R is selected from the group consisting of hydrogen, saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R" is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R is an =alkylene radical with which oxygen and sulfur form a cyclic compound with the tin atom, said cyclic compound containing from 5 to 8 members in the nucleus, the number of carbon atoms in each of R, R and R" being in the range of 1 to 12, the number of carbon atoms in R'" being in the range of 2 to 12, when Z is selected from the group consisting of fluorine, chlotine, bromine, iodine, R'CH=CHCH R", and SR, x is an integer from 0 to 2 and y is an integer such that x+y=4, and when Z is selected from the group consisting of =S, =0, O- 'O and S RIII S y is 1 and x is 2; and recovering a polymer having a reduced tendency to cold flow in the unvulcanized state.

4. In a process for making a polymer wherein a polymerization mixture is formed by polymerizing 1,3-butadiene in the presence of a hydrocarbon diluent with an organolithium catalyst, said polymerization occurring at a temperature in the range of 100 to 250 F. and at a pressure suflicient to maintain said polymerization mixture substantially in the liquid phase, the improvement which comprises terminating the polymerization reaction by adding to said polymerization mixture a compound having the formula R SnZ wherein R is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, Z is selected from the group consisting of fluorine, chlorine, bromine, iodine,

wherein R is selected from the group consisting of hydrogen, saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R" is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R'" is an alkylene radical with which oxygen and sulfur form a cyclic compound with the tin atom, said cyclic compound containing from 5 to 8 members in the nucleus, the number of carbon atoms in each of R, R, and R" being in the range of 1 to 12, the number of carbon atoms in R being in the range of 2 to 12, when Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, RCH=CHCH -OR", and AR", x is an integer from 0 to 2 and y is an integer such that x+y=4, and when Z is selected from the group consisting of =S, =0, OR"'0 and -S- y is 1 and x is 2; said compound being added in the range of 0.05 to 2 equivalents of component Z per equivalent of lithium in the catalyst; and recovering 16 a polymer having a reduced tendency to cold flow in the unvulcanized state.

5. In a process for making a polymer wherein a polymerization mixture is formed by polymerizing 1,3-butadiene and styrene in the presence of a hydrocarbon diluent with an organolithium catalyst, said polymerization occurring at a temperature in the range of 100 to 250 F. and at a pressure suflicient to maintain said polymerization mixture substantially in the liquid phase, the improvement which comprises terminating the polymerization reaction by adding to said polymerization mixture a compound having the formula: R SnZ wherein R is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, RCH=CHCH OR", =SR, =S, =0, -O--R"'O-- and -SR"'--S-, wherein R is selected from the group consisting of hydrogen, saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R" is selected from the group consisting of saturated aliphatic, saturated cycloaliphatic and aromatic radicals, R' is an alkylene radical with which oxygen and sulfur form a cyclic compound with the tin atom, said cyclic compound containing from 5 to 8 members in the nucleus, the number of carbon atoms in each of R, R' and R" being in the range of 1 to 12, the number of carbon atoms in R'" being in the range of 2 to 12, when Z is selected from the group consisting of fluorine, chlorine, bromine, iodine, R'--CH=CHCH OR, and SR, x is an integer from 0 to 2 and y is an integer such that x+y=4, and when Z is selected from the group consisting of =S, =0, -OR"O and S-- "-S, y is 1 and x is 2; said compound being added in the range of 0.05. to 2 equivalents of component Z per equivalent of lithium in the catalyst; and recovering a polymer having a reduced tendency to cold flow in the unvulcanized state.

6. A process of claim 4 in which said compound is stannic chloride.

7. A process of claim 4 in which said compound is tetraallyltin.

8. A process of claim 4 in which said compound is butyltrichlorotin.

9. A process of claim 4 in which said compound is dichlorodioctyltin.

10. A process of claim 4 in which said compound is dibutyltin sulfide.

11. A process of claim 5 in which said compound is stannic chloride.

12. A process of claim 4 in which said organolithium catalyst is n-butyllithium.

13. A process of claim 5 in which said organolithium catalyst is n-butyllithium.

14. A process of claim 4 in which said compound is dibutyldimethoxytin.

15. A rocess of claim 4 in which said compound is dibutyl(dilaurylthio)tin.

16. A process of claim 4 in which said compound is 2,2-dibutyl-5-methyl-1,3-dioxa-2-stannacyclopentane.

17. The polymer prepared by the process of claim 1.

18. The polymer prepared by the process of claim 4.

19. The polymer prepared by the process of claim 5.

References Cited UNITED STATES PATENTS 3,225,122 12/ 1965 Stumpe 260-851 3,236,821 2/1966 Strobel 26079.5

JOSEPH L. SCHOFER, Primary Examiner.

D. K. DENENBERG, Assistant Examiner. 

